Bicyclic Amines Research Articles

The synthesis of indolizidine and quinolizidine ring systems by free radical cyclization of 4-aza-6-methoxycarbonyl-5-hexenyl radicals

The formation of bicyclic amines by the intramolecular cyclization of 4-aza-6-methoxycarbonyl-5-hexenyl radicals is described. The direct attachment of a nitrogen atom to the double bond changes the electronic nature of the alkene such that the cyclization is less efficient than the all carbon analogue or the other aza-substituted 5-hexenyl cyclizations.The reaction has been used in a short, convenient synthesis of a variety of indolizidines from methyl nicotinate. In addition, the cyclization was used as the key step in a short synthesis of (±)-epilupinine from methyl nicotinate.

ChemInform Abstract: Synthesis of Five‐Membered Heterocycles from Maleimides.

AbstractMono‐ and bicyclic heterocyclic amines are prepared from 2‐cyano‐3‐methoxymaleimide (III) or 2,3‐dichloromaleimide (X) as shown in the reaction scheme.

ChemInform Abstract: Derivatives of 1,2,3,3‐Tetramethyl‐2‐azabicyclo(2.2.2)octan‐5‐trans‐ol with Antiarrhythmic and Other Activities. Part 7.

AbstractThe bicyclic amine (I) mentioned in the title reacts with the isocyanates (II) to give the ureas (III).

Menschutkin reactions of bicyclic aliphatic amines and of pyridine derivatives with methyl iodide. Extended Brönsted treatements and isokinetic relationships in acetonitrile–methanol

The rate constants, activation parameters for the Menschutkin reactions for five bases with methyl iodide, and the enthalpies of solution for the relevant species of the reactions have been determined in acetonitrile-methanol. The bases are quinuclidine, 1,4-diazabicyclo[2.2.2]octane, and 4-cyano-, 4-t-butyl-, and 4-dimethylamino-pyridine. The coefficients of empirical energy correlations defined in terms of ‘more physical’ energies, extended Bronsted treatments, αphys, and isokinetic temperatures, βphys, have been determined for these reactions. Discussion is provided on the physical meaning of these coefficients in relation to the characteristics of the activated complex.

ChemInform Abstract: 2,3‐Rearrangement of 2‐Aza‐ to 2,3‐Diazabicycles in Redox Reactions of Their N‐Nitroso and N‐Amino Derivatives.

AbstractThe bicyclic amine (I) is converted into the nitros ‐ amine (II), which on treatment with LiAlH4 and ethyl chlorocarbonate (III) gives (IV).

Structural and magnetic studies of bis(.mu.-olato) dinuclear compounds of copper(II) with bicyclic amine alcohols

Determination des structures cristallines des complexes [{Cu(eta)(ClO 4 )} 2 ]•2CH 3 OH avec eta=(tetraaza-1,3,5,7 bicyclo [3.3.1] nonanyl-3) ethanolate, [{Cu(eta)(dmso)} 2 ] (ClO 4 ) 2 avec dmso=dimethylsulfoxyde, [{Cu(etam)(dmso)} 2 ] (ClO 4 ) 2 avec etam=derive methoxymethyl-7 de l'eta et [{Cu(pta)(ClO 4 )} 2 ] avec pta=analogue propanolate-3 de l'eta. Mesures de susceptibilite magnetique

Barriers to inversion at nitrogen in bicyclic amines and hydrazines

Nitrogen inversion barriers have been measured for 7-chloro-1,7-diazabicyclo-[2.2.1] heptane and [2.2.2]octane; the unusual nature of the bridging nitrogen in bicyclo [2.2.11 systems is discussed.

Unusual deshielding of 15N in bicyclic amines and hydrazines

The bridging nitrogen in 7-aza- and 1,7-diazabicyclo[2 2.1]heptanes and unsaturated derivatives shows unusually large deshielding in the 15N NMR.

Synthesis of 3-Noradamantamine

Abstract Bridgehead primary amines in the bicyclic and tricyclic category have served as important intermediates in organic synthesis. When transformed into azo compounds, they can be used as a source of bridgehead free radicals.1 These amines also serve as precursors of azides which, when subjected to photolysis, lead to bridge-head imines (limits of Bredt's rule).2 The N,N-dichloro derivatives undergo skeleton rearrangements in the presence of strong Lewis acids resulting in ring expansion with incorporation of nitrogen.3 Bicyclic and tricyclic bridgehead amines and their derivatives exhibit a wide spectrum of pharmacodynamical properties.4

Effect of hydrogen bonding on the π-electronic absorption spectra of some bicyclic secondary amines

Spectral shift and change in the intensity of electronic absorption bands of bicyclic molecules, 1,2,3,4-tetrahydroquinoline (THQ) and 1,2,3,4-tetrahydroisoquinoline (THIQ), on hydrogen bond formation in binary and ternary solutions were investigated. Roles of factors contributing to the spectral changes such as change in configuration of the molecules and σ–π interaction are discussed in this paper.

ChemInform Abstract: PROTON AFFINITIES AND IONIZATION ENERGIES OF BICYCLIC AMINES AND DIAMINES. EFFECTS OF RING STRAIN AND OF 3‐ELECTRON Σ BONDING

Chemischer InformationsdienstVolume 13, Issue 3 Physical Organic Chemistry ChemInform Abstract: PROTON AFFINITIES AND IONIZATION ENERGIES OF BICYCLIC AMINES AND DIAMINES. EFFECTS OF RING STRAIN AND OF 3-ELECTRON Σ BONDING R. W. ALDER, R. W. ALDERSearch for more papers by this authorR. J. ARROWSMITH, R. J. ARROWSMITHSearch for more papers by this authorA. CASSON, A. CASSONSearch for more papers by this authorR. B. SESSIONS, R. B. SESSIONSSearch for more papers by this authorE. HEILBRONNER, E. HEILBRONNERSearch for more papers by this authorB. KOVAC, B. KOVACSearch for more papers by this authorH. HUBER, H. HUBERSearch for more papers by this authorM. TAAGEPERA, M. TAAGEPERASearch for more papers by this author R. W. ALDER, R. W. ALDERSearch for more papers by this authorR. J. ARROWSMITH, R. J. ARROWSMITHSearch for more papers by this authorA. CASSON, A. CASSONSearch for more papers by this authorR. B. SESSIONS, R. B. SESSIONSSearch for more papers by this authorE. HEILBRONNER, E. HEILBRONNERSearch for more papers by this authorB. KOVAC, B. KOVACSearch for more papers by this authorH. HUBER, H. HUBERSearch for more papers by this authorM. TAAGEPERA, M. TAAGEPERASearch for more papers by this author First published: January 19, 1982 https://doi.org/10.1002/chin.198203039Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume13, Issue3January 19, 1982 RelatedInformation

Proton affinities and ionization energies of bicyclic amines and diamines. Effects of ring strain and of 3-electron .sigma. bonding

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTProton affinities and ionization energies of bicyclic amines and diamines. Effects of ring strain and of 3-electron .sigma. bondingRoger W. Alder, Richard J. Arrowsmith, Alan Casson, Richard B. Sessions, Edgar Heilbronner, Branka Kovac, Hanspeter Huber, and Mare TaageperaCite this: J. Am. Chem. Soc. 1981, 103, 20, 6137–6142Publication Date (Print):October 1, 1981Publication History Published online1 May 2002Published inissue 1 October 1981https://doi.org/10.1021/ja00410a026RIGHTS & PERMISSIONSArticle Views296Altmetric-Citations65LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (677 KB) Get e-Alerts Get e-Alerts

Anatoxin-a interactions with cholinergic synaptic molecules.

Anatoxin-a, a bicyclic amine isolated from blue-green alga, binds to the nicotinic acetylcholine receptor of Torpedo electric tissue, thereby inducing conformational changes in the postsynaptic receptor--ion channel complex as evidenced by alterations in the binding of radiolabeled ligands to the complex. Anatoxin-a binds to the acetylcholine recognition site (Kd = 0.1--0.2 microM) as indicated by its competitive inhibition of specific [3H]acetylcholine and d-[3H]tubocurarine binding, Anatoxin-a stimulates the binding of three physiologically identified "ion channel blockers," [3H]perhydrohistrionicotoxin, [3H]phencyclidine, and [3H]phencyclidine methiodide. The 50% effective doses for these effects range from 0.14 to 0.28 microM. Incubation of Torpedo membranes with anatoxin-a before addition of a radiolabeled channel probe produces a time- and concentration-dependent attenuation of the binding compared to the situation in which anatoxin-a and the probe are added simultaneously. The time course for the elaboration of this decrease corresponds to electrophysiological measurements of anatoxin-a-induced desensitization of neuromuscular junction responses. In these nicotinic actions, anatoxin-a is about as potent as acetylcholine. Anatoxin-a has relatively low affinity for the muscarinic acetylcholine receptors of rat brain, inhibiting 3-[3H]quinuclidinyl benzilate binding (10(-10) M) by 50% at concentrations between 10 and 20 microM. In contrast to classical muscarinic agonists, anatoxin-a displays little regional selectivity in its binding, and its receptor affinity is unaltered by alkylation of the neural membranes with N-ethylmaleimide.

Effect of solvent in the photoreduction and quenching of benzophenone by triethylamine, 1-azabicyclo[2.2.2]-octane and 1,4-diazabicyclo[2.2.2]octane

Photoreduction of benzophenone by triethylamine (TEA) is efficient in tert-butyl alcohol, acetone and acetonitrile (ϕ = 0.8 – 1.1) and somewhat less efficient in benzene in which evidence of a light-absorbing quenching transient (LAT) is found. Photoreduction by the bridgehead bicyclic amine quinuclidine (1-azabicyclo[2.2.2]octane (ABCO)) is less efficient (ϕ = 0.08 – 0.22) with lower quantum yield in the polar solvents and higher quantum yield in the less polar solvents despite formation of a LAT. Photoreduction by the corresponding bridgehead bicyclic diamine 1,4-diazabicyclo[2.2.2]octane (DABCO) is still less efficient (ϕ = < 0.001 – 0.09) again with lower quantum yield in the polar solvent and the higher in the hydrocarbon. In 1:1 water—pyridine photoreduction of 4-carboxybenzophenone by TEA is efficient (ϕ ketyl = 1) by ABCO is very inefficient (ϕ ketyl = 0.0004) and by DABCO leads only to quenching. Low quantum yields for the reduction by ABCO and DABCO in polar solvents are accompanied by high values of the interaction rate constant k ir. The results are interpreted in terms of charge transfer interaction between excited triplet carbonyl and non-bonding electrons of the amines. The effects of hyperconjugation and charge delocalization in the charge transfer complex (CTC) and the role of charge transfer complexation and of disproportionation and dissociation to free ions as light-wasting processes are discussed.

Photochemical reactions of 6-cyanophenanthridine 5-oxide.

The photolysis of 6-cyanophenanthridine 5-oxide (1) in various solvents was reported. In addition to the expected 6-cyanodibenz [d, f] [1, 3] oxazepine (2), two new types of rearrangement products : 5-alkoxyphenanthridin-6 (5H)-one (3), as a byproduct in the photolyses using an aprotic solvent, were obtained in the present experiments. In order to account for the formation of these products (3 and 9), reasonable assumptions that the oxygen walk process from the oxaziridine species (11) leading to the oxazepine (2) is relatively inhibited to occur and thus 11 has a longer life time as compared to the related oxaziridines derived from α-cyanated bicyclic amine N-oxides were proposed. A mechanistic rationalization and characteristic features in the photochemical rearrangement reactions of 1 are discussed in detail, together with the structure determinations of the photoproducts.

双環状アミン体から中環状アミン類の合成

Conversion of bicyclic amines into medium-sized ring amines (tertiary and secondary) by selective cleavage of C-N or C-C bond is reviewed.The effectiveness of 9a- or 8a-substituents on quinolizidines or indolizidines in the above conversion is described.

Homoallylic interaction between a nitrogen lone pair and a non-adjacent π-bond. Part 6. Nature of the lone-pair electrons in n,π-homoconjugated aliphatic amines

In order to elucidate the nature of the lone-pair electrons involved in the n,π-homoconjugative system, u.v. absorption spectra have been obtained for several cyclic and bicyclic amines containing a non-adjacent benzene ring. The spectra of bishomobenzylic n,π-interacting systems (1,2,3,4-tetrahydro-1,4-iminonaphthalene derivatives) are different from those of homobenzylic systems (1,2,3,4-tetrahydroisoquinoline derivatives). We have also studied the charge-transfer complexes of iodine with various cyclic and bicyclic amines containing non-adjacent π-groups and shown that iodine–amine charge-transfer absorption is a useful means of assigning the n-orbital ionizations in the photoelectron spectra of amines. Differences in the nature of the lone-pair electrons between bishomoallylic and homoallylic n,π-interacting systems and between bishomobenzylic and homobenzylic n,π-interacting systems are discussed in relation to homoconjugation.

Studies on the proton and carbon-13 contact shifts for .sigma.-bonded molecules. Stereospecific electron spin transmission in cyclic and bicyclic amines

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTStudies on the proton and carbon-13 contact shifts for .sigma.-bonded molecules. Stereospecific electron spin transmission in cyclic and bicyclic aminesIsao Morishima, Kenichi Yoshikawa, and Koji OkadaCite this: J. Am. Chem. Soc. 1976, 98, 13, 3787–3793Publication Date (Print):June 1, 1976Publication History Published online1 May 2002Published inissue 1 June 1976https://doi.org/10.1021/ja00429a009RIGHTS & PERMISSIONSArticle Views39Altmetric-Citations18LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (723 KB) Get e-Alerts Get e-Alerts

Homoallyl interaction between the nitrogen lone pair and the nonadjacent .pi.-bond in cyclic and bicyclic amines. V. The stereospecific orientation of the lone pair electrons in 7-azanorbornene derivatives

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHomoallyl interaction between the nitrogen lone pair and the nonadjacent .pi.-bond in cyclic and bicyclic amines. V. The stereospecific orientation of the lone pair electrons in 7-azanorbornene derivativesKenichi Yoshikawa, Katsutoshi Bekki, Masanori Karatsu, Koji Toyoda, Tetsuki Kamio, and Isao MorishimaCite this: J. Am. Chem. Soc. 1976, 98, 11, 3272–3281Publication Date (Print):May 1, 1976Publication History Published online1 May 2002Published inissue 1 May 1976https://doi.org/10.1021/ja00427a037RIGHTS & PERMISSIONSArticle Views162Altmetric-Citations23LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (979 KB) Get e-Alerts Get e-Alerts

The temperature dependence of saturated amine fluorescence

The temperature dependence of fluorescence intensity of several saturated amines was studied. For “flexible” amines such as triethylamine (TEA), dimethylethylamine (DMEA), triethylemine, tri- n-octylamine (TOA), and N-methylpiperidine (NMP), it was found that I f increased as the temperature was increased. For example, in DMEA, I f increases by a factor of ca. 77 between −100 and 100°C. These results are interpreted in terms of an activated configurational change from the initially-formed (nonfluorescent) state to a relaxed (fluorescent) state in these compounds. Activation energies for these conversions range from about 1.8 kcal/mole for TOA to about 4.3 kcal/mole for TEA. Rigid, bicyclic amines having bridgehead N-atoms such as 1-azabicyclo [2.2.2] octane (ABCO) and its [3.3.3] analog were found to have temperature independent fluorescence intensities. These results were assumed to reflect the difference in energetics between the initially-formed and relaxed states relative to the “flexible” amines.